JP2003172990A - Silver halide emulsion and silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide emulsion having low fog, high sensitivity and high contrast, less liable to a change of sensitivity due to a varied humidity condition in exposure and excellent in wet wear resistance, latent image stability and reciprocity law aptitude at high illuminance. <P>SOLUTION: The silver halide emulsion has been chemically sensitized with a compound of formula (1) (where A is O, S or NR<SP>4</SP>; R<SP>1</SP>-R<SP>4</SP>are each H or a substituent; R<SP>3</SP>, together with R<SP>1</SP>or R<SP>2</SP>, may form a 5- to 7-membered cyclic structure; L is a compound capable of coordination with Au through N, S, Se or Te; and n is 0 or 1). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion, and more specifically, it has low fog, high sensitivity, high contrast, excellent reciprocity law characteristics at high illuminance, small sensitivity fluctuation due to difference in exposure conditions, and resistance to wetting. The present invention relates to a silver halide emulsion having excellent abrasion resistance.

[0002]

2. Description of the Related Art In recent years, with respect to color photographic paper, demands for performance such as high sensitivity, high image quality, and toughness during processing have been increasing. There is a demand for an emulsion having a small amount of photographic properties, an emulsion having little variation in photographic properties due to differences in temperature and humidity conditions during exposure, and an emulsion having excellent wet abrasion resistance. On the other hand, recently, with the widespread use of laser scanning exposure apparatuses, suitability for exposure with high illuminance in a short time is also one of the important performances. The major features of laser scanning exposure are that exposure can be speeded up and resolution can be improved. However, if this is used for color photographic paper, it will last for a very short time (specifically 10 seconds).
^-6 seconds) and exposure suitability under high illuminance is required.

The gold sensitization method is an effective means for achieving high sensitivity. It has long been known to use Au (III) compounds such as chloroauric acid. Although chloroauric acid is sufficiently stable in an aqueous solution, it is insufficient in terms of sensitivity, gradation, suitability for exposure to high illuminance, sensitivity fluctuation during storage, wet abrasion resistance, and toughness against temperature and humidity environment during exposure. It is photographic and needs improvement. A gold (I) compound containing a mesoionic ligand (hereinafter referred to as a mesoionic gold (I) compound) is known as a gold compound used for gold sensitization.
-267249 discloses that it is useful for the production of emulsions with high sensitivity and high contrast. However, JP-A-11-218
Mesoionic Gold (I), as disclosed in US Pat.
Compounds are known to have problems with stability in solution. Since the stability in a solution is an essential condition for stable production of an emulsion of constant quality, improvement has been desired. As one of the solutions to this problem, JP-A-11
No. 218870 proposes a method utilizing a gold (I) complex of a mercapto compound. Although this gold sensitizer has been improved in terms of solution stability, it is still a compound that decomposes and is not a sufficient solution.
Further, since it provides insufficient photographic properties in terms of wet abrasion resistance and toughness against a temperature and humidity environment at the time of exposure, improvement has been desired.

Chemical sensitization using gold sulfide colloid is one of the useful sensitization methods which have been known for a long time as can be seen from the disclosure of Au ₂ S in US Pat. No. 2,642,361.
Is one. In addition to the above U.S. patents, research disclosure (Research
Disclosure) 37154, 1995. This gold sulfide colloid sensitization method, as described in JP-A No. 11-218870, has a lot of variations and problems of giving undesired sensitometric characteristics. Further, there is a problem that preparation of the gold sulfide colloid requires a lot of time and cost.

As another example, Japanese Patent Publication No. 45-292.
74, a gold sensitization method with mercaptoglucoside gold (I) is described. But mercaptoglucoside gold (I)
Is excellent in high sensitivity and high illuminance exposure suitability, but further improvement is desired in that photographic properties are affected by fluctuations in conditions during exposure. Japanese Unexamined Patent Publication (Kokai) No. 8-69074 discloses an Au (I) complex in which thioglucose and phosphorus are coordinated. However, since the photographic property is affected by the fluctuation of the conditions during exposure, the It was desired to improve. Japanese Unexamined Patent Publication (Kokai) No. 8-69075 discloses a gold (I) salt of a mercapto compound having a substituent, which has a sulfur atom and an O, S, N atom through a methylene group as in the present invention. No specific disclosure of a compound having an acetal structure was made, and it was not sufficient in terms of sensitivity, suitability for exposure to high illuminance, and toughness due to changes in conditions during exposure. Therefore, a specific solution that satisfies the various photographic properties described above and does not have the above problems has been desired.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is low fog, high sensitivity, high contrast, small sensitivity fluctuation due to difference in exposure conditions, excellent wet abrasion resistance, and reciprocity law characteristics at high illuminance. It is to provide an excellent silver halide emulsion.

[0007]

The above objects have been achieved by the following means.

[1] A silver halide emulsion chemically sensitized with a compound represented by the following general formula (1). General formula (1)

[0009]

[Chemical 2]

[In the formula (1), A represents O, S, or NR ⁴ , and R ^{1 to} R ⁴ represent a hydrogen atom or a substituent. R ³ may form a 5- to 7-membered cyclic structure together with R ¹ or R ² . L represents a compound capable of coordinating with gold through a nitrogen atom, a sulfur atom, a selenium atom or a tellurium atom.
n represents 0 or 1. [2] The silver halide emulsion according to claim ¹ , wherein R ³ together with R ¹ or R ^{2 in the} general formula (1) forms a 5- to 7-membered cyclic structure. [3] The silver halide as described in [1] or [2], which has a silver iodochloride phase of 0.01 to 0.50 mol% per mol of total silver in the shell portion of the silver halide grain. emulsion. [4] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one layer of the silver halide emulsion layer is at least one compound represented by the general formula (1). A silver halide photographic light-sensitive material comprising a silver halide emulsion chemically sensitized by.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The silver halide color photographic light-sensitive material of the present invention will be described in detail below. First, the compound represented by formula (1) used in the present invention will be described in detail.

The substituent represented by R ^{1 to} R ⁴ is a halogen atom, an alkyl group (including a cycloalkyl group or a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group or a bicycloalkenyl group), an alkynyl group, Aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Groups, amino groups (including anilino groups), acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkyl and arylsulfonylamino groups, mercapto groups (including salts thereof) ), Alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group,
Alkyl and aryl sulfinyl groups, alkyl and aryl sulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups,
Examples include phosphinyl group, phosphinyloxy group, phosphinylamino group, and silyl group.

More specifically, a halogen atom (eg, chlorine atom, bromine atom, iodine atom), an alkyl group [straight chain,
It represents a branched, cyclic, substituted or unsubstituted alkyl group. An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms,
For example, methyl, ethyl, n-propyl, isopropyl,
t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl). , 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms). Groups such as bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2]
2,2] octane-3-yl), and further includes a tricyclo structure having many ring structures. The alkyl group in the substituents described below (for example, an alkyl group of an alkylthio group) also represents an alkyl group having such a concept. ], An alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Alkenyl group (preferably substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl group (preferably substituted or unsubstituted group having 3 to 30 carbon atoms) A cycloalkenyl group, that is, having 3 to 30 carbon atoms
Is a monovalent group obtained by removing one hydrogen atom from the cycloalkene. For example, 2-cyclopenten-1-yl, 2-
Cyclohexen-1-yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, hydrogen atom of bicycloalkene having one double bond) Is a monovalent group obtained by removing one of the groups such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl)]. , An alkynyl group (preferably having 2 to 30 carbon atoms)
A substituted or unsubstituted alkynyl group such as ethynyl, propargyl, trimethylsilylethynyl group, an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl). , O-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, which is a monovalent group obtained by removing one hydrogen atom). And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2
-Thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 30 carbon atoms).
A substituted or unsubstituted alkoxy group, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms). Aryloxy groups such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy groups (preferably having 3 to 20 carbon atoms).
A silyloxy group of, for example, trimethylsilyloxy,
t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), acyloxy Group (preferably formyloxy group, having 2 to 30 carbon atoms)
A substituted or unsubstituted alkylcarbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy) ,
Carbamoyloxy group (preferably having 1 to 30 carbon atoms)
A substituted or unsubstituted carbamoyloxy group, for example,
N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy,
N, N-di-n-octylaminocarbonyloxy, N
-N-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy,
t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyl). Oxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, carbon number 1)
To 30 substituted or unsubstituted alkylamino group, C6 to 30 substituted or unsubstituted anilino group, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (Preferably, a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, Lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino) , N, N-Dimethyla Bruno carbonylamino, N, N
-Diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n- Octadecyloxycarbonylamino,
N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 3 carbon atoms)
0 substituted or unsubstituted aryloxycarbonylamino group, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably having 0 to 10 carbon atoms) 30 substituted or unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn
-Octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably having 1 to 3 carbon atoms).
0-substituted or unsubstituted alkylsulfonylamino, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,3.
5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), a mercapto group (and a salt thereof are included. Here, the salt is, for example, Li, Na, K or R.
b, Cs and the like alkali metal salts, Mg and Ca and the like alkaline earth metal salts, gold salts and the like), alkylthio groups (preferably substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, such as methylthio, Ethylthio, n-
Hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably having 2 to 30 carbon atoms). A substituted or unsubstituted heterocyclic thio group, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio, a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-
Dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl,
N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl groups (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms,
6 to 30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Alkylsulfonyl group, a substituted or unsubstituted 6 to 30 arylsulfonyl group, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably formyl group, having 2 to 30 carbon atoms). A substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarboxyl Boniru), aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, e.g., phenoxycarbonyl, o- chlorophenoxycarbonyl, m
-Nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n- Octadecyloxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N
-Dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, and 3 carbon atoms) To 30 substituted or unsubstituted heterocyclic azo groups such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo, imide groups (preferably N-succinimide, N
-Phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably having 2 to 30 carbon atoms). 30 substituted or unsubstituted phosphinyl groups, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy groups (preferably substituted or unsubstituted phosphinyl having 2 to 30 carbon atoms) An oxy group, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphine Finylamino, dimethylaminophosphinylamino) A silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, e.g., trimethylsilyl, t- butyl dimethylsilyl, phenyldimethylsilyl) represent.

Among the above functional groups, those having a hydrogen atom may be substituted with the above group after removing the hydrogen atom.

R ^{1 to} R ⁴ may have a substituent, examples of which are the same as the above-mentioned substituents. R
Of the substituents ^{1 to} R ⁴ may have, preferably a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a carboxyl group, an alkoxy group, and aryl. Oxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group,
Aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfonyl group, acyl group,
Aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group and the like, more preferably halogen atom, alkyl group, alkenyl group. , Aryl group, heterocyclic group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, amino group, acylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl Groups, sulfo groups, alkyl and aryl sulfonyl groups, acyl groups, carbamoyl groups and the like.

In the formula (1), R ¹ and R ² are preferably hydrogen atom, alkyl group, aryl group, heterocyclic group, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, amino group and mercapto group ( And a salt thereof), an alkylthio group, an arylthio group, a heterocyclic thio group, and the like, more preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, and the like, and most preferably a hydrogen atom or an alkyl group.

In the formula (1), R ³ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or the like,
More preferred are alkyl groups, aryl groups and heterocyclic groups, and most preferred are alkyl groups or aryl groups. In formula (1), R ⁴ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, an alkyl- or arylsulfonylamino group, an alkyl- or arylsulfonyl group, an acyl group. , An aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, and the like, more preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, and the like.

In the formula (1), R ³ may form a 5- to 7-membered ring structure together with R ¹ or R ² . The cyclic structure formed at this time is a non-aromatic oxygen-containing, sulfur-containing or nitrogen-containing heterocycle. Further, this cyclic structure may form a condensed ring structure with an aromatic or non-aromatic carbon ring or an aromatic or non-aromatic heterocycle. In the present invention, it is preferred that R ³ together with R ¹ or R ² form a 5- to 7-membered cyclic structure.

In the formula (1), L represents a compound capable of coordinating with gold through a nitrogen atom, a sulfur atom, a selenium atom or a tellurium atom. Specifically, substituted or unsubstituted amines, 5- or 6-membered nitrogen-containing heterocycles, thiols, thioethers, disulfides, thioamides, selenols, selenoethers, diselenides, selenoamides, tellurols , Telluroethers, ditellurides, telluroamides and the like.

In the formula (1), when L is an amine, it is preferably a primary, secondary, or tertiary alkylamine having 1 to 30 carbon atoms, or 6 to 30 carbon atoms.
And substituted or unsubstituted primary, secondary, or tertiary anilines.

In the formula (1), when L is a 5- or 6-membered nitrogen-containing heterocycle, the heterocycle is nitrogen, oxygen,
A 5- or 6-membered nitrogen-containing heterocycle consisting of a combination of sulfur and carbon can be mentioned. Further, this nitrogen-containing heterocycle may have a substituent, and typical examples of the substituent include the same substituents as those mentioned above for R ^{1 to} R ⁴ . This nitrogen-containing heterocycle may be coordinated to gold via a nitrogen atom in the heterocycle, or, when it has a substituent, may be coordinated to gold via this substituent. L is preferably benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, benzoxazoline, oxazole, thiadiazole, oxadiazole, triazine, pyrrole, pyrrolidine, imidazolidine, morpholine, And the like, and more preferably benzotriazole, triazole, tetrazole, and indazole, and most preferably benzotriazole.

The thiol compound represented by L in the formula (1) is specifically an alkylthiol, an arylthiol, or a heterocyclic thiol. Further, these thiol compounds may be substituted, and typical examples of the substituents are the same as those mentioned above as the substituents which R ^{1 to} R ⁴ may have.

In the formula (1), the alkyl group of the alkylthiol compound represented by L has 1 to 30 carbon atoms.
A substituted or unsubstituted, straight-chain, branched or cyclic one, preferably an alkyl group having 1 to 20 carbon atoms.

In the formula (1), the aryl group contained in the arylthiol compound represented by L has 6 to 30 carbon atoms.
A substituted or unsubstituted, monocyclic or condensed ring aryl group, for example, a phenyl group or a naphthyl group. It is preferably a substituted or unsubstituted phenyl group.

In the formula (1), the heterocyclic group of the heterocyclic thiol compound represented by L is a substituted or unsubstituted 5- to 7-membered ring containing at least one of nitrogen atom, oxygen atom and sulfur atom. And a saturated or unsaturated heterocycle. These may be a single ring or may form a condensed ring together with other aryl ring or hetero ring. The heterocyclic group is preferably a 5- or 6-membered one, for example, a pyrrolyl group, a pyrrolidinyl group, a pyridyl group,
Piperidyl group, piperazinyl group, imidazolyl group, pyrazolyl group, pyrazinyl group, pyrimidinyl group, triazinyl group, triazolyl group, tetrazolyl group, quinolyl group,
Examples include isoquinolyl group, indolyl group, indazolyl group, benzimidazolyl group, pyranyl group, chromenyl group, thienyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, benzoxazolyl group, benzothiazolyl group, morpholino group and morpholinyl group. To be

The thioether represented by L in the formula (1) is a thioether compound in which an alkyl group, an aryl group, or a heterocyclic group is bonded to a sulfur atom. It may be present, and specific examples thereof include dialkyl thioethers, diaryl thioethers, diheterocyclic thioethers, alkyl-aryl thioethers, alkyl-heterocyclic thioethers, and aryl-heterocyclic thioethers. The alkyl group, aryl group and heterocyclic group of the thioether compound represented by L may be substituted, and typical examples of the substituents are the substituents that R ^{1 to} R ⁴ may have. The same as those listed as.

In the formula (1), the alkyl group contained in the thioether compound represented by L is a substituted or unsubstituted, linear, branched or cyclic group having 1 to 30 carbon atoms, preferably 1 carbon atom. To 20 alkyl groups.

In the formula (1), the aryl group contained in the thioether compound represented by L is a substituted or unsubstituted monocyclic or condensed ring aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. It is a base. It is preferably a substituted or unsubstituted phenyl group.

In the formula (1), the heterocyclic group contained in the thioether compound represented by L is a nitrogen atom, an oxygen atom,
It is a substituted or unsubstituted, saturated or unsaturated heterocycle having a 5- to 7-membered ring containing at least one of sulfur atoms. These may be a single ring or may form a condensed ring together with other aryl ring or hetero ring. The heterocyclic group is preferably a 5- or 6-membered one, for example, a pyrrolyl group, a pyrrolidinyl group, a pyridyl group, a piperidyl group, a piperazinyl group, an imidazolyl group, a pyrazolyl group, a pyrazinyl group, a pyrimidinyl group, a triazinyl group,
Examples thereof include quinolyl group, isoquinolyl group, indolyl group, indazolyl group, benzimidazolyl group, pyranyl group, chromenyl group, thienyl group, oxazolyl group, thiazolyl group, benzoxazolyl group, benzothiazolyl group, morpholino group and morpholinyl group.

Preferred thioether compounds in the present invention are symmetrical or asymmetrical dialkyl thioethers,
Diaryl thioethers and alkyl-aryl thioethers.

The disulfide represented by L in the formula (1) is a disulfide compound in which an alkyl group, an aryl group or a heterocyclic group is bonded to a sulfur atom, and the disulfide compound may be symmetrically substituted or asymmetrically substituted with respect to the disulfide group. It may be present, and specific examples thereof include dialkyl disulfides, diaryl disulfides, diheterocyclic disulfides, alkyl-aryl disulfides, alkyl-heterocyclic disulfides, and aryl-heterocyclic disulfides. The preferred disulfide in the present invention is
Symmetrical or asymmetrical dialkyl disulfides, diaryl disulfides or alkyl-aryl disulfides. The alkyl group, aryl group, and heterocyclic group of the disulfide compound represented by L may be substituted, and typical substituents are R ^{1 to} R ⁴ previously.
The same as those mentioned as examples of the substituent which may have.

In the formula (1), the alkyl group, aryl group or heterocyclic group contained in the disulfide compound represented by L has the same meaning as in the case where L is a thioether compound, and the preferred range is also the same.

In the formula (1), when L is a thioamide, the thioamide group may be a part of the ring structure or an acyclic thioamide group. Useful thioamides include, for example, US Pat. No. 4,030,925.
Issue 4,031,127, Issue 4,080,207
Nos. 4,245,037, 4,255,511
Nos. 4,266,031 and 4,276,36
No. 4 and Research Disclosure (Research D
isclosure) Volume 151, November 1976, 1516
2 and 176, December 1978, 1762.
It can be selected from those disclosed in Section 6. When L is a thioamide, preferred thioamide compounds are thiourea, thiourethane, dithiocarbamic acid ester, and 4
-Thiazolin-2-thione, thiazolidine-2-thione, 4-oxazoline-2-thione, oxazolidine-
2-thione, 2-pyrazolin-5-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, isorhodanine, 2-thio-2,4-oxazolidinedione, thiobarbituric acid, tetrazoline-5-thione , 1,2,4-triazoline-3-thione, 1,
3,4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2
-Thione, benzoxazoline-2-thione, benzothiazoline-2-thione and the like, which may be further substituted.

The selenol compound represented by L in the formula (1) is specifically an alkyl selenol, an aryl selenol, or a heterocyclic selenol. Further, these selenol compounds may be substituted, and typical examples of the substituents include the same ones as the substituents that R ^{1 to} R ⁴ may have.

In the formula (1), the alkyl group of the alkylselenol compound represented by L has 1 to 30 carbon atoms.
A substituted or unsubstituted, straight-chain, branched or cyclic one, preferably an alkyl group having 1 to 20 carbon atoms.

In the formula (1), the aryl group of the arylselenol compound represented by L has 6 to 30 carbon atoms.
A substituted or unsubstituted, monocyclic or condensed ring aryl group, for example, a phenyl group or a naphthyl group. It is preferably a substituted or unsubstituted phenyl group.

In the formula (1), the heterocyclic group of the heterocyclic selenol compound represented by L is a substituted or unsubstituted 5- to 7-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. And a saturated or unsaturated heterocycle. These may be a single ring or may form a condensed ring together with other aryl ring or hetero ring. The heterocyclic group is preferably a 5- or 6-membered one, for example, a pyrrolyl group, a pyrrolidinyl group, a pyridyl group,
Piperidyl group, piperazinyl group, imidazolyl group, pyrazolyl group, pyrazinyl group, pyrimidinyl group, triazinyl group, triazolyl group, tetrazolyl group, quinolyl group,
Examples include isoquinolyl group, indolyl group, indazolyl group, benzimidazolyl group, pyranyl group, chromenyl group, thienyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, benzoxazolyl group, benzothiazolyl group, morpholino group and morpholinyl group. To be

In the formula (1), the selenoe represented by L
The ether compound has an alkyl group, an aryl group, and a heterocyclic group.
It is a selenoether compound bonded to a selenium atom,
Even symmetric substitution with respect to the ren atom
May be, specifically, dialkyl selenoethers, dialkyl
Aryl selenoethers, diheterocyclic selenoethers
, Alkyl-aryl selenoethers, alkyl-
Heterocyclic selenoethers, aryl-heterocyclic seleno
Examples thereof include ethers. Preferred in the present invention
The selenoether compound is a symmetrical or asymmetrical dial
Killselenoethers and diarylselenoethers
Specifically, they are alkyl-aryl selenoethers. Well
In addition, the alkyl group of the selenoether compound represented by L
Group, aryl group and heterocyclic group may be substituted.
As a typical substituent, R ¹~ R^FourMay have
Examples of the substituent include the same ones.

In the formula (1), the alkyl group, aryl group or heterocyclic group of the selenoether compound represented by L has the same meaning as in the case where L is a thioether compound, and the preferred range is also the same.

The compound having a diselenide group represented by L in the formula (1) is a diselenide compound in which an alkyl group, an aryl group or a heterocyclic group is bonded to a selenium atom, and even if the diselenide group is symmetrically substituted. It may be asymmetrical substitution, specifically, dialkyl diselenides, diaryl diselenides, diheterocyclic diselenides, alkyl-aryl diselenides, alkyl-heterocyclic diselenides, aryl-heterocyclic diselenides. And so on. Preferred diselenides according to the invention are symmetrical or asymmetrical dialkyl diselenides, diaryl diselenides or alkyl-aryl diselenides. The alkyl group, aryl group and heterocyclic group of the diselenide compound represented by L may be substituted, and typical examples of the substituents are the substituents that R ^{1 to} R ⁴ may have. The same as those listed as.

In the formula (1), the alkyl group, aryl group or heterocyclic group contained in the diselenide compound represented by L has the same meaning as in the case where L is a thioether compound, and the preferred range is also the same.

When L is a selenoamide compound in the formula (1), examples of L include compounds in which a sulfur atom is replaced by a selenium atom when L is a thioamide compound.

The tellurol compound represented by L in the formula (1) is specifically an alkyl tellurol, an aryl tellurol, or a heterocyclic tellurol. Further, these tellurol compounds may be substituted, and typical examples of the substituent include the same ones as the substituents which R ^{1 to} R ⁴ may have.

In the formula (1), the alkyl group contained in the alkyl tellurol compound represented by L has 1 to 30 carbon atoms.
A substituted or unsubstituted, straight-chain, branched or cyclic one, preferably an alkyl group having 1 to 20 carbon atoms.

In the formula (1), the aryl group of the aryltellurol compound represented by L has 6 to 30 carbon atoms.
A substituted or unsubstituted, monocyclic or condensed ring aryl group, for example, a phenyl group or a naphthyl group. It is preferably a substituted or unsubstituted phenyl group.

In the formula (1), the heterocyclic group of the heterocyclic tellurol compound represented by L is a substituted or unsubstituted 5- to 7-membered ring containing at least one of nitrogen atom, oxygen atom and sulfur atom. And a saturated or unsaturated heterocycle. These may be a single ring or may form a condensed ring together with other aryl ring or hetero ring. The heterocyclic group is preferably a 5- or 6-membered one, for example, a pyrrolyl group, a pyrrolidinyl group, a pyridyl group,
Piperidyl group, piperazinyl group, imidazolyl group, pyrazolyl group, pyrazinyl group, pyrimidinyl group, triazinyl group, triazolyl group, tetrazolyl group, quinolyl group,
Examples include isoquinolyl group, indolyl group, indazolyl group, benzimidazolyl group, pyranyl group, chromenyl group, thienyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, benzoxazolyl group, benzothiazolyl group, morpholino group and morpholinyl group. To be

In the formula (1), the telluroether compound represented by L is a telluroether compound in which an alkyl group, an aryl group and a heterocyclic group are bonded to a tellurium atom, and even if the tellurium atom is symmetrically substituted. It may be asymmetrical substitution, and specifically, dialkyl telluroethers, diaryl telluroethers, diheterocyclic telluroethers, alkyl-aryl telluroethers, alkyl-
Examples thereof include heterocyclic telluroethers and aryl-heterocyclic telluroethers. Preferred telluroether compounds in the present invention are symmetrical or asymmetrical dialkyl telluroethers, diaryl telluroethers or alkyl-aryl telluroethers. Also,
The alkyl group, aryl group and heterocyclic group of the telluroether compound represented by L may be substituted,
Representative examples of the substituent include the same as those mentioned above as the substituents that R ^{1 to} R ⁴ may have.

In the formula (1), the alkyl group, aryl group or heterocyclic group contained in the telluroether compound represented by L has the same meaning as in the case where L is a thioether compound, and the preferred range is also the same.

The compound having a ditelluride group represented by L in the formula (1) is a ditelluride compound in which an alkyl group, an aryl group or a heterocyclic group is bonded to a tellurium atom, and even if the ditelluride group is symmetrically substituted. It may be asymmetrical substitution, and specifically, dialkyl ditellurides, diaryl ditellurides, diheterocyclic ditellurides, alkyl-aryl ditellurides, alkyl-heterocyclic ditellurides, aryl-heterocyclic ditellurides. And so on. Preferred ditellurides according to the invention are symmetrical or asymmetrical dialkylditellurides, diarylditellurides or alkyl-arylditellurides. The alkyl group, aryl group and heterocyclic group which the ditelluride compound represented by L may have may be substituted, and typical examples of the substituent include those which R ^{1 to} R ⁴ may have. The same as those listed as.

In the formula (1), the alkyl group, aryl group or heterocyclic group contained in the ditelluride compound represented by L has the same meaning as in the case where L is a thioether compound, and the preferred range is also the same.

In the formula (1), when L is a telluroamide compound, examples of L include compounds in which a sulfur atom is replaced by a tellurium atom when L is a thioamide compound.

In the present invention, L is preferably a 5- or 6-membered nitrogen-containing heterocycle, thiols, thioethers, thioamides, selenoethers or selenoamides, and more preferably 5- or 6-membered nitrogen-containing heterocycles. Heterocycles, thiols, thioethers or thioamides, most preferably thiols, thioethers or thioamides. In the present invention, L is
It is not a ligand that coordinates to Au at the phosphorus atom. It is presumed that the P ligand strongly binds to Au (I) and affects the formation of sensitized nuclei. In fact, those having a P ligand are not preferable in terms of exposure temperature dependency and latent image stability.

In the formula (1), n represents 0 or 1. In the present invention, n is preferably 0.

In the present invention, among the compounds represented by the formula (1), preferred one is A represents O or S,
R ¹ and R ² are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group and a heterocyclic thio group, and R ³ is a hydrogen atom, An alkyl group, an aryl group,
Heterocyclic group-Yes, R ⁴ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, an alkyl and arylsulfonylamino group, an alkyl and arylsulfonyl group, an acyl group, and n is 0 or 1
And when n is 1, L represents a thioether, a thioamide, or a 5- to 6-membered nitrogen-containing heterocycle. More preferably, A represents O or S, R ¹ and R ² are a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ³ is an alkyl group, an aryl group or a heterocyclic group, and R ⁴ is A hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, n is 0 or 1, and n is 1
Then L represents thioethers or thioamides. Most preferably A represents O or S,
R ¹ and R ² are a hydrogen atom, an alkyl group or an aryl group,
R ³ is an alkyl group or an aryl group, R ⁴ is a hydrogen atom,
It is an alkyl group, an aryl group, or a heterocyclic group, and n is 0. Of these, particularly preferable in the present invention, the cyclic structure formed by R ³ together with R ¹ or R ² is glucofuranose, glucopyranose, galactopyranose, galactofuranose, mannopyranose,
This is the case of sugar derivatives such as loxopyranose and derivatives in which the oxygen atom in the cyclic structure is replaced with a sulfur atom, among which glucofuranose, galactopyranose, galactofuranose, mannopyranose, lysopyranose, etc. Is preferred. Examples of preferable compounds include thiomannose gold (I) salt, thiogalactose gold (I) salt, thiolyxose gold (I) salt and the like. In the present invention, the general formula (1) is disclosed in JP-B-45-.
It does not represent the mercaptoglucoside gold (I) salt described in 29274. We are Japanese Patent Publication Sho 45-292
The mercaptoglucoside gold (I) described in 74 was synthesized and examined in combination with the compound of the present invention. Japanese Patent Examination Sho 45-2
In 9274, the steric structure of the anomeric position is unknown. We succeeded in separating and quantifying α-type and β-type by applying that the steric structure of sugar anomeric position is distinguished by observing NMR of anomeric proton. From this, it was revealed that the one prepared by the synthesis method described in Japanese Examined Patent Publication No. 45-29274 is a mixture of stereoisomers whose main component is β-form. We examined the mercaptoglucoside gold (I) described in JP-B-45-29274 and the compound of the present invention, and as shown in Examples later, JP-B-4
The mercaptoglucoside gold (I) described in 5-29274 was successful in achieving photographic performance not obtained. The performance of the above-mentioned gold (I) mercaptoglucoside is also superior to the conventionally well-known gold-sulfur sensitization such as the combination of chloroauric acid and hypo. However, there is a problem with the properties of β-mercaptoglucoside gold (I).

Specific examples of the compound represented by the general formula (1) are shown below. However, the present invention is not limited to these. Further, with respect to a compound having a plurality of stereoisomers, the stereostructure thereof is not limited (the photographic performance may vary depending on the stereostructure).

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

The compound represented by the general formula (1) of the present invention can be synthesized by various known methods. Since the most suitable synthetic method is selected depending on the individual compound, a general synthetic method cannot be mentioned. Among them, a useful synthetic route will be explained.

(Synthesis of Exemplified Compound 1-1) 1-Thio-β
0.5 g of -D-glucose tetraacetate was dissolved in 5 ml of methylene chloride, and a solution of 0.4 g of gold tetrahydrothiophene chloride complex in 10 ml of methylene chloride was added. After stirring for 30 minutes at room temperature, the total volume is reduced to about 1 by vacuum concentration.
It was set to / 3. 20 ml of ethanol was added thereto, and the precipitated crystals were collected by filtration to obtain 0.4 g of Exemplified compound 1-1. (Synthesis of Exemplified Compound 1-4) Known Method (Carbohydrate
Research, 81 (1980) 261-274).
S- (2,3,4,6-tetra-O-acetyl-α-D
-Mannopyranosyl) -2-thiosudurea hydrobromide (1.5 g) was added to a solution of 30 ml of methanol in 2.5 ml of sodium methoxide (28% methanol solution), and the mixture was stirred at room temperature for 12 hours. After adding 5 ml of water to 370 mg of the formed precipitate, a solution of 472 mg of sodium chloroaurate and 436 mg of thiodiethanol in 18 ml of ethanol was added dropwise, and the mixture was stirred for 30 minutes. The α-thiomannose gold (I) salt (Exemplified Compound 1-
4) was obtained in an amount of 470 mg. (Synthesis of Exemplified Compound 1-5) Exemplified Compound 1-5 was synthesized according to Scheme 1. Scheme 1

[0061]

[Chemical 3]

(Synthesis of Synthetic Intermediate 1) A solution of 4.1 g of pentamethylene sulfide in 100 ml of carbon tetrachloride was ice-cooled, and 5.6 g of N-chlorosuccinimide was added. After stirring under ice cooling for 2 hours, the insoluble matter was filtered off, and a solution of 3.2 g of thiourea in 75 ml of acetone was added to the filtrate. After stirring at room temperature for 1 hour, 7 g of Synthetic intermediate 1 was obtained by collecting the precipitated solid by filtration. (Synthesis of Synthetic Intermediate 2) 4 g of sodium hydroxide and 17 g of Synthetic Intermediate 17 were dissolved in 80 ml of water while cooling with ice and stirred for 2 hours. 50% of 2 mol / l hydrochloric acid while cooling with ice
ml was added, and 100 ml of methylene chloride was added for extraction. After washing the organic layer with a saturated aqueous sodium hydrogen carbonate solution,
It was dried over sodium sulfate and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography to obtain 4 g of Synthetic intermediate 2. (Synthesis of Exemplified Compound 1-5) 0.2 g of a synthetic intermediate was dissolved in 10 ml of chloroform and then 0.2 m of triethylamine was added.
1 was added. Then, a solution prepared by dissolving 491 mg of gold tetrahydrothiophene complex in 10 ml of chloroform was added. The reaction solution was concentrated under reduced pressure and recrystallized from methanol to obtain 0.8 g of Exemplified compound 1-5.

The addition amount of the compound represented by the general formula (1) of the present invention may vary widely depending on the case, but is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻³ mol per mol of silver halide. , And more preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol.

The compound represented by the general formula (1) of the present invention is water or alcohols (methanol, ethanol etc.), ketones (acetone etc.), amides (dimethylformamide etc.), glycols (methyl propylene). Glycol) and esters (ethyl acetate etc.) are preferably added as a solvent. In addition, characteristics such as sensitivity, gradation, suitability for high-illuminance exposure, and humidity dependency at the time of exposure will be described in combination with known techniques in Examples described later regarding advantages of the present invention. It is preferable in terms of temperature dependence and latent image stability.

The compound represented by the general formula (1) of the present invention can be added at any stage during emulsion production, but it is added after the formation of silver halide grains and before the end of the chemical sensitization step. It is preferable.

The silver halide grains in the silver halide emulsion used in the present invention are preferably cubic or tetradecahedral crystal grains having substantially {100} faces (these grains have rounded vertexes and higher grains). May have the following planes) or octahedral crystal grains, or 50 of the total projected area
A tabular grain having an aspect ratio of 2 or more and 200 or less and having at least 100% of {100} planes or {111} planes is preferable. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of particles. In the present invention, a cube or {1
A tabular grain having a {00} plane as a main plane or a tabular grain having a {111} plane as a main plane is preferably applied.

As the silver halide emulsion used in the present invention, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsion and the like are used. From the viewpoint of rapid processability, silver chloride is used. A silver chloride, silver chlorobromide, silver chloroiodide or silver chlorobromoiodide emulsion having a content of 90 mol% or more is preferable, more preferably a silver chloride content of 95 mol% or more, further preferably 98 mol%. The above silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsions are preferred. Among such silver halide emulsions,
In the present invention, the shell portion of the silver halide grain,
Those having a silver iodochloride phase content of 0.01 to 0.50 mol%, more preferably 0.05 to 0.40 mol% per mol of total silver are preferred because high sensitivity can be obtained and the exposure to high illuminance is excellent. Further, those having a silver bromide localized phase of 0.2 to 5 mol%, more preferably 0.5 to 3 mol% based on the total silver mol on the surface of the silver halide grain can obtain high sensitivity and It is particularly preferable because the photographic performance can be stabilized.

When the emulsion of the present invention contains silver iodide, the iodide ion can be introduced by adding a solution of iodide salt alone or by adding a silver salt solution and a high chloride salt solution. An iodide salt solution may be added. In the latter case, the iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the iodide salt and the high chloride salt. The iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth iodide salt. Alternatively, US Pat. No. 5,389,5
Iodide can also be introduced by cleaving the iodide ion from the organic molecule described in No. 08. Further, fine silver iodide grains can be used as another iodide ion source.

The addition of the iodide salt solution may be concentrated at one stage of grain formation or may be conducted over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fog. When the iodide ion is introduced inside the emulsion grains, the increase in sensitivity is small. Therefore, the addition of the iodide salt solution is preferably performed outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 80%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. When the addition of the iodide salt solution is completed slightly inside the grain surface, an emulsion having higher sensitivity and lower fog can be obtained.

The distribution of the iodide ion concentration in the grain in the depth direction was determined by etching / TOF-SIMS (Time of Flight).
Secondary Ion Mass Spectrometry) method, for example, TRIFT II TOF-SIMS manufactured by Phi Evans. The TOF-SIMS method is specifically described in "Surface Analysis Technology Selection Manual, Secondary Ion Mass Spectrometry" edited by The Surface Science Society of Japan, Maruzen Co., Ltd. (issued in 1999). When the emulsion grains are analyzed by the etching / TOF-SIMS method, it can be analyzed that the iodide ions are exuded toward the grain surface even after the addition of the iodide salt solution is completed inside the grains. When the emulsion of the present invention contains silver iodide, the iodide ion has a maximum concentration on the surface of the grain and the iodide ion concentration decreases toward the inside, as analyzed by an etching / TOF-SIMS method. Is preferred.

When the emulsion of the present invention contains a silver bromide localized phase.
In this case, the silver bromide content is at least 10 mol% or more.
It is made by epitaxially growing a localized phase on the grain surface.
And are preferred. The silver bromide content of the silver bromide localized phase is 10 to 10.
A range of 60 mol% is preferable, and a range of 20 to 50 mol% is preferable.
Is most preferred. The silver bromide localized phase is a halo in the present invention.
0.1 to 5 mol% of the total amount of silver constituting the silver genide grains
Is preferably composed of 0.3 to 4 mol%
More preferably, it is composed of silver. Silver bromide station
During the existing phase, iridium (III) chloride and bromine
Rhodium (III), second iridium chloride (IV), hexa
Sodium chloroiridium (III), hexachloro
Potassium iridium (IV), hexaammine iridium
(IV) salt, trioxalatoiridium (III) salt, g
Group VIII metal complexes such as lyoxalatoiridium (IV) salts
It is preferable to contain on. Addition of these compounds
The addition amount is wide depending on the purpose, but silver halide 1
10 per mole^-9-10 ^-2Molar is preferred.

In the present invention, a transition metal ion may be added in the process of forming and / or growing a silver halide grain to incorporate the metal ion into the inside and / or the surface of the silver halide grain. The metal ion used is preferably a transition metal ion, among which iron, ruthenium, iridium, osmium, lead, cadmium,
Alternatively, it is preferably zinc. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion,
It is preferable to use thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thionitrosyl ion, and the above iron, ruthenium, iridium, osmium, lead, It is also preferable to use it by coordinating with any metal ion of cadmium or zinc, and it is also preferable to use plural kinds of ligands in one complex molecule. Also,
An organic compound can be used as the ligand, and preferred organic compounds include a chain compound having a main chain having 5 or less carbon atoms and / or a 5-membered or 6-membered heterocyclic compound. More preferable organic compound is a compound having a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom in the molecule as a coordination atom to a metal, and most preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazan, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds having these compounds as a basic skeleton and substituents introduced into them are also preferable.

Suitable as a combination of metal ion and ligand
More preferably, iron and ruthenium ions and cyanide
It is a combination of ions. In these compounds
Anion ions to the central metal iron or ruthenium
It is preferable that the majority of the coordination numbers of
Coordination sites are thiocyan, ammonia, water and nitrosyl.
On, dimethyl sulfoxide, pyridine, pyrazine, or
Alternatively, it is preferably occupied by 4,4'-bipyridine.
Most preferably, all six coordination sites of the central metal are cyan
Hexacyanoiron complex or hex
Forming a sacyan ruthenium complex. these
Complexes with cyanide ion as a ligand are
1 x 10 per mole^-81 x 10 from mole^-2Adding moles
Is preferred, 1 × 10^-65 × 10 from a mole^-FourAdding moles
Is most preferred. When iridium is used as the central metal
In this case, the ligand is preferably fluoride ion or chloride.
Ion, bromide ion, iodide ion, among them
Preference is given to using chloride or bromide ions
Yes. Specifically, the iridium complex is preferably [IrC
l₆]^3-, [IrCl₆]^2-, [IrCl_Five(thiazole)]^2-, [IrCl_Five(5-CH
₃-thiazole)]^2-, [IrCl_Five(H₂O)]^2-, [IrCl_Five(H₂O)]^-, [Ir
Cl_Four(H₂O)₂]^-, [IrCl_Four(H₂O)₂]⁰, [IrCl₃(H₂O)₃] ⁰, [IrCl
₃(H₂O)₃]⁺, [IrBr₆]^3-, [IrBr₆]^2-, [IrBr_Five(H₂O)]^2-,
[IrBr_Five(H₂O)]^-, [IrBr_Four(H₂O)₂]^-, [IrBr_Four(H₂O)₂]⁰, [Ir
Br₃(H₂O)₃]⁰, And [IrBr₃(H₂O)₃]⁺Is. these
Iridium complex is 1 x 10 per mol of silver during grain formation^-Ten
1 x 10 from mole^-3It is preferable to add a mole, 1 × 10^-8
1 x 10 from mole^-FiveMost preferably, it is added in moles. Le
When the central metals are thenium and osmium,
Trosyl ion, thionitrosyl ion, or water molecule
It is also preferable to use both and chloride ions as ligands.
Yes. More preferably pentachloronitrosyl complex, pen
Tachlorothionitrosyl complex or pentachloroa
Form a hexachloro complex.
It is also preferable to make it. These complexes are
1 x 10 per mole^-Ten1 x 10 from mole^-6Mole addition
And more preferably 1 × 10^-91 x 10 from mole^-6
It is to add a mole.

In the present invention, the above complex is added directly to the reaction solution at the time of silver halide grain formation, or to an aqueous halide solution for forming silver halide grains, or to a solution other than that. It is preferably incorporated into the silver halide grain by adding it to the grain forming reaction solution. Further, it is also preferable to combine these methods to incorporate them in the silver halide grains.

When these complexes are incorporated into silver halide grains, it is preferable that they are uniformly present inside the grains, but JP-A-4-208936 and JP-A-2-12524.
5, as disclosed in JP-A-3-188437, it is also preferable that the particles are present only in the particle surface layer,
It is also preferable that the complex is present only inside the particles and a layer not containing the complex is added to the surface of the particles. Also, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, it is possible to modify the surface phase of particles by physically aging them with fine particles in which a complex is incorporated. preferable. Further, these methods can be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. There is no particular limitation on the halogen composition at the position where the complex is contained, and the complex may be contained in any of the silver chloride layer, the silver chlorobromide layer, the silver bromide layer, the silver iodochloride layer and the silver iodobromide layer. Is also preferable.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use two or more kinds of the above monodisperse emulsions having different average grain sizes by blending them in the same layer, or to perform multilayer coating.

The silver halide emulsion used in the present invention includes various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) are also preferably used.

In the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A-11-109576 and JP-A-11-32709.
Adjacent to the carbonyl group described in No. 4, cyclic ketones having a double bond in which both ends are substituted with an amino group or a hydroxyl group (particularly represented by the general formula (S1), paragraphs 0036 to 0071) Can be incorporated into the specification of the present application), sulfo-substituted catechols and hydroquinones described in JP-A No. 11-143011 (for example, 4,
5-dihydroxy-1,3-benzenedisulfonic acid,
2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,3
-Dihydroxybenzene sulfonic acid, 2,5-dihydroxybenzene sulfonic acid, 3,4,5-trihydroxybenzene sulfonic acid and salts thereof), represented by the general formula (A) of US Pat. No. 5,556,741. Hydroxylamines (The description of US Pat. No. 5,556,741 from column 4, line 56 to column 11, line 22 is preferably applied to the present application and incorporated as a part of the specification of the present application. , And the water-soluble reducing agents represented by formulas (I) to (III) of JP-A No. 11-102045 are preferably used in the present invention.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, Heterocyclic compounds-Cyanine by FM Harmer.
dyes andrelated compounds (John Wiley & Sons [New
York, London] 1964). As specific examples of compounds and the spectral sensitization method, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A-3-123 is known.
The spectral sensitizing dye described in JP-A No. 340 is very preferable from the viewpoint of stability, strength of adsorption, temperature dependence of exposure and the like.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range.

The silver halide grains used in the present invention include the conventional sulfur sensitization, in addition to the treatment with the compound according to the present invention.
At least one of chalcogen sensitization such as selenium sensitization and tellurium sensitization, noble metal sensitization such as gold sensitization and palladium sensitization, and reduction sensitization may be performed at any step of the silver halide emulsion production process. it can. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type of embedding a chemically sensitized nucleus inside the grain, a type of embedding at a shallow position from the grain surface, and a type of forming a chemically sensitized nucleus on the surface. In the emulsion of the present invention, the location of the chemically sensitized nuclei can be selected according to the purpose, but generally preferred is the case where at least one chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations that can be preferably used in combination is chalcogenide sensitization and noble metal sensitization, either alone or in combination, and described by TH James, The Photographic Process, 4th Edition, Macmillan. Published by company, 1
977, (TH James, The Theor
y of the Photographic Pro
cess, 4th ed, Macmillan, 197
7) It can be carried out using active gelatin as described on pages 67 to 76, and Research Disclosure, Vol. 120, April 1974, 12008; Research Disclosure, Vol. 34, June 1975,
13452, U.S. Pat. Nos. 2,642,361 and 3,2.
97,446, 3,772,031, 3,85
7,711, 3,901,714, 4,26
6,018, and 3,904,415, and pAg 5-10, pH 5-8, and temperature 30-80 ° C as described in GB 1,315,755 for sulfur, selenium, and tellurium. , Gold, platinum, palladium, iridium or combinations of these sensitizers. In noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used,
Of these, gold sensitization, palladium sensitization, and a combination of both are particularly preferable.

Conventional selenium sensitizers that can be used in combination are
It is possible to use the selenium compound disclosed in the known patent.
it can. Usually, unstable selenium compounds and / or non-
Unstable selenium compounds can be added at high temperatures and
Use by stirring the emulsion at 40 ° C or higher for a certain time
Can be As unstable selenium compounds, Japanese Patent Publication No. 44
-15748, JP-B-43-13489, JP-A-4
-25832, JP-A-4-109240, etc.
It is preferable to use the compound of Used in the present invention
The amount of selenium sensitizer added depends on the activity of the selenium sensitizer used.
Degree, type and size of silver halide, aging temperature and time
Although it varies depending on the time period, it is preferable that one silver halide is used.
2 x 10 per le^-6More than 5 × 10^-6It is the following. Sele
The temperature of the chemical sensitization when a sensitizer is used is preferably
It is 40 ° C. or higher and 80 ° C. or lower. pAg and
And pH are arbitrary. For example, for pH 4-9
The effect of the present invention can be obtained in a wide range. Also this
As a gold sensitizer for gold sensitization that can be used in combination with
It may be +1 valent or +3 valent, and is usually used as a gold sensitizer.
It is possible to use a gold compound. As a typical example
Are, for example, chloroaurate, potassium chloroaurate, o
-Ric trichloride, potassium auric thiocyanate
Nate, potassium iodoaurate, tetracyanoau
Rick acid, ammonium aurothiocyanate, pi
Lysyl trichlorogold, gold sulfide, gold selenide
You can The amount of gold sensitizer added varies depending on various conditions
However, as a guide, 1 x 10 per mol of silver halide^-7
More than mol and 5 × 10 ^-FiveLess than a mole is preferred
Yes.

In the chemical sensitization of the present invention, it is desirable to use sulfur sensitization together. For sulfur sensitization, known compounds as sulfur sensitizers can be used. For example, thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. In addition, for example, U.S. Pat. Nos. 1,574,944 and 2,410,689,
No. 2,278,947, No. 2,728,668
No. 3, No. 3,501,313, No. 3,656,95
5, German Patent 1,422,869, Japanese Patent Publication No. 56-
The sulfur sensitizers described in JP-A-24937 and JP-A-55-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but is 1 × 10 ⁻⁷ mol or more per 5 mol of silver halide and 5 × 10 ^−5. It is preferably not more than mol.

In the chemical sensitization of the silver halide emulsion of the present invention, gold sensitization known in the art can be additionally used. By performing gold sensitization, the sensitivity of the emulsion can be increased, and fluctuations in photographic performance upon scanning exposure with laser light or the like can be reduced. As gold sensitization that can be used in combination, gold sulfide colloid sensitization, gold (I) complexes having various inorganic gold compounds and inorganic ligands, and gold (I) compounds having organic ligands can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and examples of the gold (I) complex having an inorganic ligand include a gold dithiocyanate compound such as potassium gold (I) dithiocyanate and gold (I) 3 dithiosulfate. Compounds such as sodium dithiosulfate compounds such as sodium can be used.

Examples of the gold (I) compound having an organic ligand include bis-gold (I) mesoionic heterocycles described in JP-A-4-267249, such as gold (I) tetrafluoroborate bis (1,4). , 5-Trimethyl-1,2,4-triazolium-3-thiolate), an organic mercapto gold (I) complex described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfonate benzamide) ) Phenyl] -5-mercaptotetrazole potassium salt) Aurate (I) pentahydrate, a gold (I) compound coordinated with a nitrogen compound anion described in JP-A-4-268550, for example, bis (1-methylhydan) Toinato) gold (I) sodium salt tetrahydrate can be used. Further, a gold (I) thiolate compound described in US Pat.
-69074, JP-A-8-69075, JP-A-9-2
69554 gold compounds, US Pat. No. 56208
The compounds described in No. 41, No. 5912112, No. 5620841, No. 5939245, and No. 5912111 can also be used. The addition amount of these compounds may be varied over a wide range depending on the case, but 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ⁻⁶ mol, per mol of silver halide.
Is about 5 × 10 ⁻⁴ mol.

The silver halide photographic light-sensitive material of the present invention comprises
Conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as the photographic support. As the transmissive support, a transparent film such as a cellulose nitrate film or polyethylene terephthalate, a polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), or a polyester of NDCA, terephthalic acid and EG is used. Those provided with an information recording layer such as a magnetic layer are preferably used. As the reflection type support, a reflection support which is laminated with a plurality of polyethylene layers or polyester layers and which contains a white pigment such as titanium oxide in at least one layer of such a water resistant resin layer (laminate layer) is preferable.

Further preferred reflective supports in the present invention include those having a polyolefin layer having fine pores on the paper base on which the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no microvoids (eg polypropylene, polyethylene) and is close to the paper substrate. More preferably, it is made of a polyolefin (for example, polypropylene, polyethylene) having micropores on its side. The density of these multi-layer or single-layer polyolefin layers located between the paper substrate and the photographic constituent layers is from 0.40.
It is preferably 1.0 g / ml, and 0.50 to 0.
70 g / ml is more preferred. The thickness of these multi-layer or one-layer polyolefin layers located between the paper substrate and the photographic constituent layers is preferably 10 to 100 μm, and 15 to 100 μm.
70 μm is more preferable. The ratio of the thickness of the polyolefin layer to the thickness of the paper substrate is preferably 0.05 to 0.2,
1 to 0.5 is more preferable.

It is also preferable to provide a polyolefin layer on the opposite side (rear surface) to the photographic constituent layers of the paper base from the viewpoint of increasing the rigidity of the reflective support. In this case, the polyolefin layer on the back surface has a matte surface. Preferred are polyethylene or polypropylene, and more preferred is polypropylene. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support of the present invention, a preferred embodiment regarding the polyolefin layer provided on the paper substrate is described in JP-A-10-3.
33277, 10-333278, 11-52.
No. 513, No. 11-65024, EP0880065.
And the examples described in EP 0880066.

Further, it is preferable that the waterproof resin layer contains a fluorescent brightening agent. Further, the fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, benzoxazole-based, coumarin-based, and pyrazoline-based fluorescent whitening agents can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent whitening agents are more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . When mixed with the water resistant resin, the mixing ratio is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass based on the resin. The reflective support may be a transmissive support or a reflective support such as the one described above coated with a hydrophilic colloid layer containing a white pigment. Further, the reflection type support may be a support having a metal surface of specular reflection or type II diffuse reflection.

As the support used in the light-sensitive material according to the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. Especially, the transmission density of the support is 0.35 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 0.8.

In the light-sensitive material of the present invention, a hydrophilic colloid layer can be decolorized by a treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving image sharpness and the like. A dye (among others, an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, or a divalent to tetravalent alcohol (eg, an alcohol) is added to the water-resistant resin layer of the support. 1 part of titanium oxide surface-treated with trimethylolethane)
It is preferable to contain 2 mass% or more (more preferably 14 mass% or more).

The light-sensitive material according to the present invention has a hydrophilic colloid layer for the purpose of preventing irradiation and halation and improving safety of safelight. It is preferable to add the dyes described above, which can be decolorized by the treatment (in particular, oxonol dyes and cyanine dyes). Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes may deteriorate color separation and safelight safety when the amount used is increased. Examples of dyes that can be used without deteriorating color separation include JP-A-5-127324 and 5-1.
The water-soluble dyes described in No. 27325 and No. 5-216185 are preferable.

In the present invention, instead of the water-soluble dye,
Alternatively, a colored layer that can be decolorized by treatment with a water-soluble dye is used. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with the emulsion layer via an intermediate layer containing a processing color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to install a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (400 nm for ordinary printer exposure).
It is preferable that the optical density value is 0.2 or more and 3.0 or less at a wavelength having the highest optical density in the visible light region of up to 700 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure). It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, Japanese Patent Laid-Open No. 2-282244-3
The dyes described on page 8 from the upper right column of the page, and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method of incorporating a solid fine particle dispersion in a hydrophilic colloid layer, a method of mordanting an anionic dye with a cationic polymer, a method of halogenating the dye Examples thereof include a method of adsorbing to fine particles such as silver and fixing in a layer, a method of using colloidal silver as described in JP-A-1-239544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at a pH of 6 or less but is substantially water-soluble at a pH of 8 or more is disclosed. 2-30824
No. 4, pages 4-13. Also, for example,
A method of mordanting an anionic dye on a cationic polymer is described in JP-A-2-84637, pages 18 to 26. For the preparation method of colloidal silver as a light absorber, see US Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

The silver halide photographic light-sensitive material of the present invention is used as a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc. Among them, it is preferable to use it as a color photographic paper.
Color photographic paper is a yellow color-forming silver halide emulsion layer,
It is preferable to have at least one magenta coloring silver halide emulsion layer and at least one cyan coloring silver halide emulsion layer. Generally, these silver halide emulsion layers are yellow coloring These are a silver halide emulsion layer, a magenta coloring silver halide emulsion layer, and a cyan coloring silver halide emulsion layer.

However, a layer structure different from this may be adopted. The silver halide emulsion layer containing a yellow coupler may be arranged at any position on the support, but when the yellow coupler containing layer contains silver halide tabular grains, a magenta coupler containing halogenated It is preferably coated at a position farther from the support than at least one of the silver emulsion layer or the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by a sensitizing dye, the yellow-coupler-containing silver halide emulsion layer is located farthest from the support than other silver halide emulsion layers. It is preferably coated. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a central layer of the other silver halide emulsion layers, and from the viewpoint of reducing photofading, the cyan coupler-containing silver halide emulsion layer is The bottom layer is preferred. Further, each of the yellow, magenta and cyan color forming layers may be composed of two layers or three layers. For example, as described in JP-A-4-75055, JP-A-9-114035, JP-A-10-246940, U.S. Pat. No. 5,576,159, etc., a coupler layer containing no silver halide emulsion is used as a silver halide emulsion. It is also preferable to provide it adjacent to the emulsion layer to form a color forming layer.

The silver halide emulsion and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied in the present invention, and processing methods and processing additions applied to process the light-sensitive material. As the agent, JP-A-62-2
15272, JP-A-2-33144, European Patent EP
Those described in 0,355,660A2, particularly those described in European Patent EP0,355,660A2 are preferably used. Furthermore, JP-A-5-34
No. 889, No. 4-359249, No. 4-313753
No. 4, No. 4-270344, No. 5-66527, No. 4
-34548, 4-145433, 2-854.
Issue 1, 1-158431, 2-90145, 3
The silver halide color photographic light-sensitive materials and their processing methods described in JP-A-194539, JP-A-2-93641, European Patent Publication No. 0520457A2 and the like are also preferable.

Particularly, in the present invention, the above-mentioned reflection type support, silver halide emulsion, further different metal ion species doped in the silver halide grains, a storage stabilizer for the silver halide emulsion or an antifoggant. , Chemical sensitization method (sensitizer),
Spectral sensitization method (spectral sensitizer), cyan, magenta, and yellow couplers and their emulsion dispersion method, color image storability improving agent (anti-staining agent and anti-fading agent), dye (coloring layer), gelatin species, photosensitive material With regard to the layer structure of the above-mentioned and the pH of the coating film of the light-sensitive material, those described in each part of the patents shown in Table 4 below are particularly preferably applicable.

[0100]

[Table 4]

As the cyan, magenta and yellow couplers used in the present invention, others are described in JP-A-6-66.
No. 2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144, page 3, upper right column, line 14 to page 18 upper left column, end line and page 30 upper right. Column line 6 to page 35, lower right column line 11 and EP 0355,660A2, page 4, line 15 to line 27, page 5, line 30 to line 28, last line, page 45 line 29 to line 31. G, page 47, line 23-6
The couplers described on page 3, line 50 are also useful. The present invention also includes the general formulas (II) and (III) of WO-98 / 33760 and the general formula (D) of JP-A-10-221825.
A compound represented by the following may be added, which is preferable.

A more specific description will be given below. As a cyan coupler which can be used in the present invention, a pyrrolotriazole type coupler is preferably used, and it is disclosed in JP-A-5-31332.
The couplers represented by formula (I) or (II) of No. 4, the coupler represented by formula (I) of JP-A-6-347960, and the exemplified couplers described in these patents are particularly preferable. Phenol-based and naphthol-based cyan couplers are also preferable, and examples thereof include JP-A-10-
The cyan coupler represented by formula (ADF) described in No. 333297 is preferable. As cyan couplers other than the above, there are EP 0488248 and EP.
Pyrroloazole type cyan couplers described in 0491197A1, 2,5-diacylaminophenol couplers described in U.S. Pat. No. 5,888,716, U.S. Pat. Nos. 4,873,183 and 4,916,16. 051
Described in JP-A No. 8-1., A pyrazoloazole type cyan coupler having an electron-withdrawing group and a hydrogen bonding group at the 6-position,
No. 71185, No. 8-311360, No. 8-3390.
A pyrazoloazole type cyan coupler having a carbamoyl group at the 6-position described in No. 60 is also preferable.

Further, in addition to the diphenylimidazole type cyan couplers described in JP-A-2-33144, 3-hydroxypyridine type cyan couplers (among others, the couplers listed as specific examples) described in European Patent EP 0333185A2. (42) 4-equivalent couplers having a chlorine-releasing group to make them 2-equivalent, couplers (6) and (9) are particularly preferable) and JP-A-64-322.
Cyclic active methylene-based cyan couplers described in JP-A No. 60 (specifically, coupler example 3 listed as a specific example,
8, 34 are particularly preferred), European Patent EP 0456622.
It is also possible to use the pyrrolopyrazole type cyan couplers described in 6A1 and the pyrroloimidazole type cyan couplers described in European Patent EP0484909.

Among these cyan couplers, the pyrroloazole type cyan coupler represented by the general formula (I) described in JP-A No. 11-228138 is particularly preferable,
The description of paragraph numbers 0012 to 0059 of the patent, including the exemplary cyan couplers (1) to (47), is directly applied to the present application and is preferably incorporated as a part of the specification of the present application.

As the magenta coupler used in the present invention, 5-pyrazolone type magenta couplers and pyrazoloazole type magenta couplers as described in the publicly known documents of the above table are used, and among them, hue, image stability,
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6-position of a pyrazolotriazole ring as described in JP-A-61-65245 in terms of color developability, etc. -65246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and Europe. Patent No. 226,849
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. A and No. 294,785A. Particularly, as the magenta coupler, a pyrazoloazole coupler represented by the general formula (MI) described in JP-A-8-122984 is preferable, and paragraph numbers 0009 to 0026 of the patent are directly applied to the present application. Incorporated as part of the specification. In addition to this, European Patent Nos. 854384 and 8
A pyrazoloazole coupler having a steric hindrance group at both the 3-position and the 6-position described in No. 84640 is also preferably used.

Further, as the yellow coupler, in addition to the compounds described in the above table, European Patent EP0447969 may be used.
Acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in A1 specification, malondianilide type yellow couplers having a cyclic structure described in European Patent EP 0482552A1, European Published Patent No. 953870A1. No., No. 953871A1,
No. 953872A1, No. 953873A1, No. 953874A1, No. 953875A1 and the like, pyrrole-2 or 3-yl or indole.
2 or 3-ylcarbonylacetic acid anilide type coupler,
The acylacetamide type yellow coupler having a dioxane structure described in US Pat. No. 5,118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

The coupler used in the present invention is a loadable latex polymer (for example, US Pat. No. 4,2,4) in the presence (or absence) of the high boiling organic solvent described in the above table.
No. 03,716) or dissolved with a water-insoluble and organic solvent-soluble polymer to be emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449 at columns 7 to 15 and International Publication WO88 / 00723 at pages 12 to 30. The homopolymers or copolymers mentioned may be mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high molecular weight redox compounds described in JP-A-5-333501, WO98 / 33
760, phenidone and hydrazine compounds described in U.S. Pat. No. 4,923,787 and the like, JP-A-5-2496.
The white couplers described in JP-A No. 37, JP-A-10-282615 and German Patent No. 19629142A1 can be used. In addition, especially raising the pH of the developer,
In the case of accelerating development, German Patent No. 1961878
It is also preferable to use the redox compounds described in 6A1, European Patent 839623A1, European Patent 842975A1, German Patent 1980846A1 and French Patent 2760460A1.

In the present invention, a compound having a triazine skeleton having a high molar extinction coefficient is preferably used as the ultraviolet absorber, and for example, the compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or the non-photosensitive layer. JP-A-46-333
5, No. 55-152776, JP-A-5-19707.
No. 4, No. 5-232630, No. 5-307232,
6-211813, 8-53427, 8-2
No. 34364, No. 8-239368, No. 9-3106.
No. 7, No. 10-15898, No. 10-147577.
No. 10-182621, German Patent No. 197397.
97A, European Patent No. 711804A and Japanese Patent Publication No.
Compounds described in, for example, No. 501291.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As preferable gelatin, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably 5 ppm.
Or less, and more preferably 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg.
/ M ² or less, more preferably 10 mg / m ² or less, most preferably 5 mg / m ² or less. In the present invention,
In order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add an antibacterial / antifungal agent as described in JP-A-63-271247. Further, the film pH of the light-sensitive material is preferably 4.0 to 7.0, and more preferably 4.0 to 6.5.

In the present invention, a surfactant can be added to the light-sensitive material from the viewpoints of improving the coating stability of the light-sensitive material, preventing the generation of static electricity, adjusting the charge amount, and the like. Examples of the surfactant include anionic surfactants, cationic surfactants, betaine surfactants and nonionic surfactants, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. Particularly, a fluorine atom-containing surfactant can be preferably used.

The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10.
^-5 to ¹ g / m ² , preferably 1 x 10 ^-4 to 1 x 10 ^-1 g
/ M ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ^2.
Is. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but preferably in combination with other conventionally known surfactants.

The light-sensitive material of the present invention is suitable for a scanning exposure system using a cathode ray (CRT), in addition to being used for a printing system using an ordinary negative printer. A cathode ray tube exposure apparatus is simpler and more compact than an apparatus using a laser, and is low in cost. Moreover, the optical axis and color can be easily adjusted. For the cathode ray tube used for image exposure, various light-emitting bodies that emit light in the spectral region are used as necessary. For example, any one of a red light emitting body, a green light emitting body, and a blue light emitting body, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a fluorescent substance that emits light in a yellow, orange, violet, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

When the light-sensitive material has a plurality of light-sensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at once, that is, the cathode ray. Image signals of a plurality of colors may be input to the tube to cause the tube surface to emit light. A method of sequentially inputting image signals for each color to sequentially emit light of each color and exposing through a film that cuts colors other than that color (field sequential exposure)
In general, frame sequential exposure is preferable for high image quality because a high resolution cathode ray tube can be used.

The light-sensitive material of the present invention comprises a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic emission light source (SHG) in which a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal are combined.
A digital scanning exposure method using monochromatic high-density light such as is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) which is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, it is preferable to use a semiconductor laser in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention depends on the scanning used.
It can be arbitrarily set depending on the wavelength of the light source for exposure.
Solid-state laser using semiconductor laser as excitation light source
Is obtained by combining a semiconductor laser and a nonlinear optical crystal
With the SHG light source, the laser oscillation wavelength can be halved.
Therefore, blue light and green light are obtained. Therefore, the
The spectral sensitivity maximum is in the normal three wavelength regions of blue, green, and red.
It is possible to put on. In such scanning exposure
The exposure time is the pixel when the pixel density is 400 dpi.
The preferred exposure is defined by the size defined as the exposure time
10 hours ^-FourSeconds or less, more preferably 10^-6Less than a second
Below.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table. To process the light-sensitive material of the present invention, page 26, lower right column, line 1 to page 34, upper right column, line 9 of JP-A-2-207250, and page 5, upper left column of JP-A-4-97355. The processing materials and processing methods described in the 17th line to the 18th lower right column, 20th line can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The present invention is preferably applied to a light-sensitive material having rapid processing suitability. The color development time means the time from when the light-sensitive material enters the color developing solution to when it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic developing machine, etc., the time during which the photosensitive material is immersed in the color developing solution (so-called in-liquid time), and the photosensitive material leaves the color developing solution to bleach-fix in the next processing step. The total of the time during which the film is transported in the air toward the bath (so-called air time) is called the color development time. Similarly, the bleach-fixing time refers to the time from when the light-sensitive material enters the bleach-fixing solution until it enters the next washing or stabilizing bath. Further, the washing or stabilizing time means a time (so-called in-liquid time) during which the light-sensitive material enters the washing or stabilizing solution and then remains in the solution for the drying step.

When rapid processing is performed in the present invention,
The color development time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, and more preferably 30 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, and further preferably 30 seconds or less and 6 seconds or more. The washing or stabilizing time is preferably 150 seconds or less, more preferably 130 seconds.
Seconds or less and 6 seconds or more.

The method of developing the light-sensitive material of the present invention after exposure is as follows: a method of developing with a conventional developer containing an alkali agent and a developing agent, an alkaline solution containing a developing agent in the light-sensitive material and containing no developing agent. In addition to a wet method such as a method of developing with an activator solution such as, a heat development method without using a processing solution can be used. In particular, the activator method is a preferable method because the processing solution does not contain a developing agent, so that the processing solution can be easily managed and handled, and that the load at the time of processing the waste solution is small and the environment can be preserved. In the activator method, the developing agent or its precursor incorporated in the light-sensitive material is, for example, JP-A-8-234.
No. 388, No. 9-152686, No. 9-152693
Nos. 9-212814 and 9-160193 are preferred.

Further, a developing method in which the amount of silver coated on the light-sensitive material is reduced and an image amplification process (intensification process) using hydrogen peroxide is also preferably used. In particular, it is preferable to use this method as an activator method. Specifically, JP-A-8
The image forming method using an activator solution containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152695 is preferably used. In the activator method, after processing with an activator solution, desilvering processing is usually performed, but in the image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted and a simple method such as washing with water or stabilization can be performed. Further, in the method of reading image information from a light-sensitive material with a scanner or the like, it is possible to adopt a processing form which does not require desilvering processing even when a light-sensitive material having a high silver content such as a light-sensitive material for photographing is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known materials and methods can be used. Preferably Research Disclosure Item 36544
(September 1994) pp. 536-541, JP-A-8
What was described in No. 234388 can be used.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. In the present invention, as described in European Patents EP0789270A1 and EP0789480A1, before applying image information, a yellow microdot pattern may be pre-exposed and copy regulation may be applied.

The light-sensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following known materials. -Automatic printing and developing system described in JP-A-10-333253-Photosensitive material conveying device described in JP-A-2000-10206-Recording system including an image reading device described in JP-A-11-215312-JP-A-11-88619 Japanese Patent Laid-Open No. 10-2029
50. An exposure system comprising a color image recording system described in 50. A digital photo print system including a remote diagnosis system described in JP-A-10-210206. A photo print system including an image recording apparatus described in Japanese Patent Application No. 10-159187.

[0125]

EXAMPLES Example 1 (Preparation of Emulsion A Used for Blue-Sensitive Emulsion Layer) A 1: 1 mixture of cubic large size emulsion A1 having an average grain size of 0.70 μm and small size emulsion A2 having an average grain size of 0.50 μm (silver mol Ratio) to prepare Emulsion A. The coefficients of variation of the grain size distributions of Emulsions A1 and A2 were 0.09 and 0.11. In each size emulsion, 0.5 mol% of silver bromide was locally contained in a part of the surface of the grain based on silver chloride. The volume from the outermost layer of this particle is 10
% Is 0.1 mol% based on total halogen.
Iodide ion of 1 mole is present, and to 1 mol of silver halide
1 × 10 ^-6 mol of K ₄ Ru (CN) ₆ , 1 × 10 ^-7 mol of yellow blood salt per 1 mol of silver halide, 1 × per mol of silver halide
10 ⁻⁸ mol of K ₂ IrCl ₅ (H ₂ O) was present. In this emulsion, the following blue-sensitive sensitizing dyes A and B were added to Emulsion A1 per mol of silver.
3.2 × 10 ⁻⁴ mol and 4.4 × 10 ⁻⁴ mol, respectively, of Emulsion A2 and spectral sensitization.

[0126]

[Chemical 4]

(Emulsions Cl-B and I used in the green-sensitive emulsion layer)
-Preparation of B) A cubic emulsion having an average grain size of 0.40 μm and having no silver iodochloride phase in the shell was prepared. Coefficient of variation of particle size distribution is 0.0
9. 0.6 mol% of silver bromide was locally contained on the grain surface.
Similarly to Emulsion A, K ₄ Ru (CN) ₆ , yellow blood salt and K ₂ IrCl ₅ (H ₂ O) were present in the emulsion grains. Emulsion Cl as described above
-Adjusted B. Further, Emulsion IB having a silver iodochloride phase in the shell portion was prepared in the same manner as Emulsion Cl-B except that 0.1 mol% of silver iodide was contained near the grain surface. Sensitizing dye D was 3.3 × 10 ⁻⁴ mol per mol of silver halide, and sensitizing dye E was 5 × 10 ⁻⁵ per mol of silver halide.
Further, the sensitizing dye F is added in an amount of 2.
3 × 10 ⁻⁴ mol was added.

[0128]

[Chemical 5]

(Preparation of emulsion C used in the red-sensitive emulsion layer)
Cubic, large size emulsion C with average grain size 0.40 μm
1: 1 mixture of 1 and 0.30 μm small size emulsion C2
(Silver molar ratio) was adjusted. The coefficient of variation of the particle size distribution is
0.09 and 0.11. Each size emulsion has each size
Both emulsions contain 0.1 mol% silver iodide near the grain surface.
Then, 0.8 mol% of silver bromide was locally contained on the grain surface.
Also, as in Emulsion A, K_FourRu (CN)₆, Yellow blood
Salt, K₂IrCl_Five(H ₂O) was present. Sensitizing dyes G and H
For each mole of silver halide,
Then 8.0 x 10^-Five1 for moles and small emulsions
0.7 x 10^-FiveMol added. Further, the following compound I
In the red-sensitive emulsion layer 3.0 × 1 per mol of silver halide
0^-3Mol added.

[0130]

[Chemical 6]

[0131]

[Chemical 7]

(Preparation of color photographic light-sensitive material and coated sample) The surface of a support having both sides of paper coated with polyethylene resin was subjected to corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate. Is provided
Further, the photographic constituent layers of the first layer to the seventh layer were sequentially coated to prepare a sample (101) of a silver halide color photographic light-sensitive material having the layer structure shown below. The coating liquid for each photographic constituent layer is
It was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 57 g, color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
21 g of solvent (Solv-1) and 80 m of ethyl acetate
22 g of a 23.5% by mass gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate.
Emulsified and dispersed in 0 g by a high-speed stirring emulsifying machine (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the second to seventh layers are also the first layer coating solution.
Prepared in a similar manner to. As a gelatin hardening agent for each layer
Is sodium (2,4-dichloro-6-oxide-1,
3,5-triazine) (H-1), (H-2), (H-
3) was used. In addition, Ab-1, Ab-2, Ab in each layer
-3 and Ab-4 are each 15.0 mg / m in total amount.
², 60.0 mg / m², 5.0 mg / m²And 10.0
mg / m²Was added.

[0135]

[Chemical 8]

[0136]

[Chemical 9]

Next, the chemical sensitization step will be described. The milk
The agent is heated to 40 ° C and chloroauric acid and the optimum amount of sodium thiosulfate are added.
Add thorium pentahydrate, then 60 ° C-80 ° C (to emulsion
), And then add the sensitizing dye from the previous period.
After cooling to 40 ° C, 1- (3-methylureidopheny
) -5-mercaptotetrazole, respectively.
3.3 x 10 per mol of silver halide^-FourMole, 1.0 × 10^-3
Molar and 5.9 x 10 ^-FourMol added. Later shown in Table 5
The various emulsions of this example were prepared by changing the chemical sensitizer.
It was prepared by performing a sensitization step.

Further, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to each of the second, fourth, sixth and seventh layers at 0.2 mg / m 2.
² , 0.2 mg / m ² , 0.6 mg / m ² , 0.1 mg /
It was added so as to be m ² .

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7 was used.
-Tetrazaindene was added in an amount of 1 x 10 ^-4 mol and 2 x 10 ^-4 mol per mol of silver halide, respectively. Further, a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200
000-400000) in an amount of 0.05 g / m ² . In addition, catechol-in the second layer, the fourth layer and the sixth layer
Disodium 3,5-disulfonate 6 mg / each
m ² , 6 mg / m ² , and 18 mg / m ² were added. In addition, the following dyes (the amount in parentheses represents the coating amount) were added to prevent irradiation.

[0140]

[Chemical 10]

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide emulsion,
Indicates the coating amount in terms of silver. Support Polyethylene resin laminated paper [White pigment (TiO ₂ ; content 16% by mass; ZnO; content 4% by mass) and fluorescent whitening agent (4,4′-bis (5 -Methylbenzoxazolyl) stilbene, content 0.03% by mass, including bluing dye (ultimate blue)] First layer (blue-sensitive emulsion layer) Emulsion A 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 color image stabilizer (Cpd-1) 0.07 color image stabilizer (Cpd-2) 0.04 color image stabilizer (Cpd-3) 0.07 color image stabilizer (Cpd-8) 02 Solvent (Solv-1) 0.21

[0142]   Second layer (color mixing prevention layer)     Gelatin 0.99     Color mixing inhibitor (Cpd-4) 0.09     Color image stabilizer (Cpd-5) 0.018     Color image stabilizer (Cpd-6) 0.13     Color image stabilizer (Cpd-7) 0.01     Solvent (Solv-1) 0.06     Solvent (Solv-2) 0.22

[0143]   Third layer (green sensitive emulsion layer)   Emulsion Cl-B 0.14     Gelatin 1.36     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.14     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-4) 0.002     Color image stabilizer (Cpd-6) 0.09     Color image stabilizer (Cpd-8) 0.02     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.11     Solvent (Solv-4) 0.22     Solvent (Solv-5) 0.20

[0144]   Fourth layer (color mixing prevention layer)     Gelatin 0.71     Color mixing prevention layer (Cpd-4) 0.06     Color image stabilizer (Cpd-5) 0.013     Color image stabilizer (Cpd-6) 0.10     Color image stabilizer (Cpd-7) 0.007     Solvent (Solv-1) 0.04     Solvent (Solv-2) 0.16

[0145]   Fifth layer (red sensitive emulsion layer)   Emulsion C 0.12     Gelatin 1.11.     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-1) 0.05     Color image stabilizer (Cpd-6) 0.06     Color image stabilizer (Cpd-7) 0.02     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-14) 0.01     Color image stabilizer (Cpd-15) 0.12     Color image stabilizer (Cpd-16) 0.03     Color image stabilizer (Cpd-17) 0.09     Color image stabilizer (Cpd-18) 0.07     Solvent (Solv-5) 0.15     Solvent (Solv-8) 0.05

[0146]   Sixth layer (UV absorption layer)     Gelatin 0.46     UV absorber (UV-B) 0.45     Compound (S1-4) 0.0015     Solvent (Solv-7) 0.25   Seventh layer (protective layer)     Gelatin 1.00     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.02     Surfactant (Cpd-13) 0.01

[0147]

[Chemical 11]

[0148]

[Chemical 12]

[0149]

[Chemical 13]

[0150]

[Chemical 14]

[0151]

[Chemical 15]

[0152]

[Chemical 16]

[0153]

[Chemical 17]

[0154]

[Chemical 18]

[0155]

[Chemical 19]

[0156]

[Chemical 20]

In the third layer of Sample (101), the emulsion shown in Table 5 described below was used, and the chemical sensitizers in the chemical sensitization step were set as shown in Table 5, and the remaining ingredients were treated in the same manner as in Sample (101). A sample was prepared.

The following experiment was conducted to examine the photographic characteristics of these samples. Experiment 1 Sensitometry (low illuminance and high illuminance) Each coated sample was subjected to gradation exposure for sensitometry using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.). Equipped with SP-2 filter, exposure amount 200l
Exposure was performed for 10 seconds at low illuminance at x · sec (lux · sec). In addition, a high-intensity exposure sensitometer (HIshita Denso Co., Ltd. HI
E type) was used to provide gradation exposure for sensitometry. An SP-2 filter was attached and exposed to high illuminance for 10 ^-4 seconds. After the exposure, color development processing A described later was performed.

The magenta color density of each sample after the treatment was measured, and 10-second exposure low illuminance sensitivity and 10 ^-4 second exposure high illuminance sensitivity were obtained, respectively. The sensitivity was defined by the reciprocal of the exposure amount that gives a color density 1.5 higher than the minimum color density, and the relative value was defined as a relative value with the developed sensitivity of Sample (106) being 100. Further, the gradation was obtained from the slope of the line between the sensitivity point and the sensitivity point at the density of 1.5.

Experiment 2 Sensitivity to Exposure Humidity Dependence of Relative Humidity on Exposure of Each Sample to 55% and 80%
Set to. After the exposure for 1/10 seconds, the process A was performed, and the magenta color density of each sample was measured. The sensitivity was defined by the reciprocal of the exposure amount that gives a color density 0.5 higher than the minimum color density, and the relative value when the sensitivity of the sample (106) was 100 was defined as the relative sensitivity. The difference (hereinafter referred to as dS (humidity)) obtained by subtracting the relative sensitivity when exposed at 80% humidity from the relative sensitivity when exposed at 55% humidity was obtained. Experiment 3 Latent Image Stability A difference was obtained by subtracting the sensitivity in the development process immediately after exposure (10 seconds) from the sensitivity in the development process 1 hour after the exposure (hereinafter, dS (latent image)). Indicate). The sensitivity was defined as the reciprocal of the exposure amount that gives a color density 0.3 higher than the minimum color density. When dS (latent image) has a negative value, it shows that the sensitivity becomes low when the time from exposure to development processing is long, and a technique for making dS (latent image) close to zero is desired.

The results of Experiment 1, Experiment 2 and Experiment 3 are summarized in Table 5.

[0162]

[Table 5]

From Table 5, the following can be seen. The emulsion using the compound of the present invention, when exposed for 10 seconds, is a comparative compound.
Higher sensitivity than emulsions using (A) and (C). It can be seen that the sensitivity is particularly high at 10 ⁻⁴ second exposure (high illuminance exposure) and the reciprocity law characteristic is excellent. In addition, conventionally, there was a problem that the sensitivity was likely to change due to the humidity variation at the time of exposure, but it was found that the present invention has an advantage that the sensitivity variation is extremely small. The comparative compound (B) had a resistance to humidity fluctuations during exposure that was slightly closer to the compound of the present invention, but had a slightly lower sensitivity and poor latent image stability. The difference due to the sensitizing method as described above was more remarkable when the silver halide emulsion grains contained silver iodide than when they did not contain silver iodide.

The processing steps are shown below. [Processing A] The light-sensitive material 101 was processed into a roll having a width of 127 mm, imagewise exposed using a mini-lab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., and then double the color developing tank capacity in the following processing step. Until then, continuous treatment (running test) was performed. The treatment using this running liquid was designated as treatment A. Treatment process Temperature Time Replenishment amount ^* Color development 38.5 ° C. 45 seconds 45 ml Bleach fixing 38.0 ° C. 45 seconds 35 ml Rinse (1) 38.0 ° C. 20 seconds-Rinse (2) 38.0 ° C. 20 seconds − Rinse (3) ** 38.0 ° C. for 20 seconds − Rinse (4) ** 38.0 ° C. for 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Rin screening system RC50D manufactured by Fuji Photo Film Co., Ltd. The rinse liquid is taken out from the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the same tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was performed from the tank countercurrent system from (1) to (4).)

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] 800 ml water 800 ml Dimethylpolysiloxane-based surfactant 0.1g 0.1g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8g 8.8g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0g 10.0g 4,5-dihydroxybenzene-1,3- Sodium disulfonate 0.5g 0.5g Potassium chloride 10.0g- Potassium bromide 0.040g 0.010g Triazinylaminostilbene fluorescent 2.5g 5.0g Whitening agent (Hakkor FWA-SF / Showa Kagaku) Sodium sulfite 0.1g 0.1g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                     8.5g 11.1g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4 -Amino-4-aminoaniline / 3/2 sulfuric acid monohydrate                                     5.0 g 15.7 g Potassium carbonate 26.3g 26.3g Add water 1000 ml 1000 ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid)                                   10.15 12.50

[0166] [Bleach fixer] [Tank solution] [Replenisher] Water 700 ml 600 ml Ethylenediaminetetraacetate Iron (III) ammonium                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g m-carboxybenzene fulphinic acid                                       8.3g 16.5g Nitric acid (67%) 16.5g 33.0g Imidazole 14.6g 29.2g Ammonium thiosulfate (750 g / l)                       107.0 ml 214.0 ml Ammonium sulfite 16.0 g 32.0 g Ammonium bisulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted with 25 ° C / acetic acid and ammonia)                                       6.0 6.0

[0167] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μS / cm or less)                           1000 ml 1000 ml pH 6.5 6.5

Example 2 Using the emulsion prepared in Example 1, a thin sample was prepared by changing the layer structure from (101) as follows. A sample was prepared in which the emulsion of the third layer was changed in the same manner as in Example 1. Experiment 1 and Experiment 2 of Example 1 for these samples
And Experiment 3 was performed. The layer structure is shown in Sample (201).
The results are similar to the results of Example 1, and the effect of the present invention was confirmed even in the ultra-rapid treatment of the thinned sample.

[0169]   Preparation of sample 201   First layer (blue sensitive emulsion layer)     Emulsion A 0.24     Gelatin 1.25     Yellow coupler (ExY) 0.57     Color image stabilizer (Cpd-1) 0.07     Color image stabilizer (Cpd-2) 0.04     Color image stabilizer (Cpd-3) 0.07     Color image stabilizer (Cpd-8) 0.02     Solvent (Solv-1) 0.21

[0170]   Second layer (color mixing prevention layer)     Gelatin 0.60     Color mixing inhibitor (Cpd-19) 0.09     Color image stabilizer (Cpd-5) 0.007     Color image stabilizer (Cpd-7) 0.007     UV absorber (UV-C) 0.05     Solvent (Solv-5) 0.11

[0171]   Third layer (green sensitive emulsion layer)     Emulsion Cl-B 0.14     Gelatin 0.73     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.05     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-7) 0.008     Color image stabilizer (Cpd-8) 0.07     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.009     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.06     Solvent (Solv-4) 0.11     Solvent (Solv-5) 0.06

[0172]   Fourth layer (color mixing prevention layer)     Gelatin 0.48     Color mixing prevention layer (Cpd-4) 0.07     Color image stabilizer (Cpd-5) 0.006     Color image stabilizer (Cpd-7) 0.006     Ultraviolet absorber (UV-C) 0.04     Solvent (Solv-5) 0.09

[0173]   Fifth layer (red sensitive emulsion layer)     Emulsion C 0.12     Gelatin 0.59     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-7) 0.01     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-15) 0.19     Color image stabilizer (Cpd-18) 0.04     Ultraviolet absorber (UV-7) 0.02     Solvent (Solv-5) 0.09

[0174]   Sixth layer (UV absorption layer)     Gelatin 0.32     Ultraviolet absorber (UV-C) 0.42     Solvent (Solv-7) 0.08   Seventh layer (protective layer)     Gelatin 0.70     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.01     Surfactant (Cpd-13) 0.01     Polydimethylsiloxane 0.01     Silicon dioxide 0.003

Each of the samples prepared was the same as in Experiment 1 of Example 1.
Exposure was performed in the same manner as in 2 and 3, and the color development processing was an ultra-rapid processing according to the development processing B shown below.

[Processing B] The above photosensitive material was processed into a roll having a width of 127 mm, and the processing time and the processing temperature were changed by using an experimental processing device which was modified from Fuji Photo Film Co., Ltd. Imagewise exposure is performed on a photosensitive material sample from a negative film having an average density, and continuous processing (running test) is carried out until the capacity of the color developing replenisher used in the following processing steps becomes 0.5 times the capacity of the color developing tank. It was

Processing Step Temperature Time Replenishment Amount * Color development 45.0 ° C. 15 seconds 45 mL Bleach-fixing 40.0 ° C. 15 seconds 35 mL Rinse 1 40.0 ° C. 8 seconds − Rinse 2 40.0 ° C. 8 seconds − Rinse 3 ** 40.0 ° C. 8 sec-Rinse 4 ** 38.0 ° C. 8 sec 121 mL Dry 80 ° C. 15 sec (Note) * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. Attach to (3) and rinse (3)
The rinse liquid is taken out from the pump and sent to a reverse osmosis module (RC50D) by a pump. The permeated water sent in the same tank is supplied to the rinse (4), and the concentrated liquid is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinse was a 4-tank countercurrent system from (1) to (4).

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800mL 600mL Optical brightener (FL-1) 5.0 g 8.5 g Triisopropanolamine 8.8g 8.8g Sodium p-toluenesulfonate 20.0 g 20.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10g 0.50g Potassium chloride 10.0g- 4,5-dihydroxybenzene- Sodium 1,3-disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonate Ethyl) hydroxylamine 8.5 g 14.5 g 4-amino-3-methyl-N-ethyl-N- (Β-methanesulfonamidoethyl) aniline ・ 3/2 Sulfate ・ Monohydrate 10.0g 22.0g Potassium carbonate 26.3g 26.3g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.35 12.6

[0179] [Bleaching fixer] [Tank solution] [Replenisher] Water 800mL 800mL Ammonium thiosulfate (750 g / mL) 107 mL 214 mL Succinic acid 29.5g 59.0g Ethylenediaminetetraammonium iron (III) acetate 47.0g 94.0g Ethylenediaminetetraacetic acid 1.4g 2.8g Nitric acid (67%) 17.5g 35.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with nitric acid and ammonia water) 6.00 6.00

[0180] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL pH (25 ° C) 6.5 6.5

[0181]

[Chemical 21]

Example 3 Using the sample prepared in Example 2, an image was formed by laser scanning exposure. As the laser light source, a semiconductor laser GaAlAs (oscillation wavelength 808.5 nm)
YAG solid-state laser (oscillation wavelength 94
6 nm) S of LiNbO ₃ having an inversion domain structure
473 nm wavelength-converted and taken out by the HG crystal,
Semiconductor laser GaAlAs (oscillation wavelength 808.7n
LiNb having an inversion domain structure of YVO ₄ solid-state laser (oscillation wavelength 1064 nm) using m) as an excitation light source
Wavelength converted by SHG crystal of O ₃ and extracted 532
nm and AlGaInP (oscillation wavelength about 680 nm: type No. LN9R20 manufactured by Matsushita Electric Industrial Co., Ltd.) were used. The laser light of each of the three colors was moved in a direction perpendicular to the scanning direction by a polygon mirror so that the sample could be sequentially scanned and exposed. Fluctuations in the amount of light due to the temperature of the semiconductor laser are suppressed by using a Peltier device to keep the temperature constant. Effective beam diameter is 80 μm
The scanning pitch was 42.3 μm (600 dpi), and the average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds. After the exposure, the color development processing B was performed, and the same results as those of the high illuminance exposure in Examples 1 and 2 were obtained, and it was found that it is also suitable for image formation using laser scanning exposure. It was

[0183]

The emulsion of the present invention is a silver halide emulsion having high sensitivity, high contrast, small fluctuation in sensitivity due to the difference of exposure conditions, and excellent latent image stability and reciprocity law characteristics at high illuminance. Also suitable for stable production.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hirotomo Sasaki             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. F-term (reference) 2H023 BA02 BA05 CA02 CA04

Claims (4)

[Claims] 1. A silver halide emulsion chemically sensitized with a compound represented by the following general formula (1). General formula (1) [In the formula (1), A represents O, S, or NR ⁴ ,
R ^{1 to} R ⁴ represent a hydrogen atom or a substituent. R ³ may form a 5- to 7-membered cyclic structure together with R ¹ or R ² . L
Represents a compound capable of coordinating with gold through a nitrogen atom, a sulfur atom, a selenium atom or a tellurium atom. n represents 0 or 1. ] 2. In the general formula (1), R ³ is R ¹ or R ^2.
The silver halide emulsion according to claim 1, which together with it forms a 5- to 7-membered cyclic structure. 3. The silver halide according to claim 1 or 2, wherein the shell portion of the silver halide grain has a silver iodochloride phase of 0.01 to 0.50 mol% based on the total mol of silver. emulsion. 4. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers comprises a compound represented by the general formula (1). A silver halide photographic light-sensitive material comprising a silver halide emulsion chemically sensitized with at least one kind.